Preparation and properties of bio-based epoxy networks derived from isosorbide diglycidyl ether

Two bio-based epoxy prepolymers were synthesized from isosorbide, a carbohydrate-based C6 building block, using two different synthetic routes. The chemical structures of the bio-based epoxy prepolymers were analyzed by SEC, ESI-TOF MS, FTIR, ¹H NMR and ¹³C NMR analysis. The resulting epoxy prepolymers differ by the molar mass distribution, one consists of the pure epoxy monomer whereas the other exhibits various oligomeric species. A traditional petroleum-based epoxy prepolymer, DGEBA, which has similar epoxy equivalent weight, was also used in this study for comparison. Gelation and crosslinking reactions of the two bio-based epoxy precursors with an amino hardener, isophorone diamine, were studied using rheological measurements and differential scanning calorimetry (DSC) respectively; the effect of the stoichiometric ratio n_ah/n_e was investigated. Structures of the epoxy networks were evaluated using dynamic mechanical analysis (DMA) and thermo gravimetric analysis (TGA).     

Endoglin modulates cellular responses to TGF-beta 1

Endoglin is a homodimeric membrane glycoprotein which can bind the beta 1 and beta 3 isoforms of transforming growth factor-beta (TGF-beta). We reported previously that endoglin is upregulated during monocyte differentiation. We have now observed that TGF-beta itself can stimulate the expression of endoglin in cultured human monocytes and in the U-937 monocytic line. To study the functional role of endoglin, stable transfectants of U-937 cells were generated which overexpress L- or S- endoglin isoforms, differing in their cytoplasmic domain. Inhibition of cellular proliferation and downregulation of c-myc mRNA which are normally induced by TGF-beta 1 in U-937 cells were totally abrogated in L-endoglin transfectants and much reduced in the S-endoglin transfectants. Inhibition of proliferation by TGF-beta 2 was not altered in the transfectants, in agreement with the isoform specificity of endoglin. Additional responses of U-937 cells to TGF-beta 1, including stimulation of fibronectin synthesis, cellular adhesion, platelet/endothelial cell adhesion molecule 1 (PECAM-1) phosphorylation, and homotypic aggregation were also inhibited in the endoglin transfectants. However, modulation of integrin and PECAM-1 levels and stimulation of mRNA levels for TGF-beta 1 and its receptors R-I, R-II, and betaglycan occurred normally in the endoglin transfectants. No changes in total ligand binding were observed in L-endoglin transfectants relative to mock, while a 1.5-fold increase was seen in S-endoglin transfectants. The degradation rate of the ligand was the same in all transfectants. Elucidating the mechanism by which endoglin modulates several cellular responses to TGF-beta 1 without interfering with ligand binding or degradation should increase our understanding of the complex pathways which mediate the effects of this factor.     

Télé-Échographie Robotisée: des concepts à la validation clinique

Echography is an imaging modality that is very useful in many clinical situations. It requires specific medical skills, and such skills are not always available. We describe the principles of an original robotics architecture, which enables the patient to benefit from the tele-presence of a distant medical expert. We discuss how this architecture is operated, and present the principles of its clinical validation.     

POLYCYCLIC AROMATIC HYDROCARBONS BIOACCUMULATION AND BIOTRANSFORMATION PRODUCTS IN TROUT EXPOSED THROUGH FOOD PELLETS

Polycyclic aromatic hydrocarbons (PAHs) were previously measured in whole small finfish (< 30 cm) or in the internal organs relative to the rest of tissues, as well as in muscle, liver, and gonads of larger finfish, collected offshore in the Northwest Atlantic. Alkylated naphthalenes (NA) were more abundant than phenanthrenes (PA), while fluoranthene (FL), pyrene (PY), and chrysene (CH) were also detected in some cases. Bioaccumulation pointed to uptake by respiration and, probably by a dietary contribution, especially for benthic species. Therefore, speckled trout were exposed to PA, FL, and PY through food and the parent PAH and their respective metabolites were analyzed. Trout maintained at 10°C were fed daily for 10 weeks with pellets spiked with 0.33–0.38 μg of each PAH per g fish. Muscle, internal organs, and bile of fish were analyzed by HPLC every 2 weeks, for up to 14 weeks. The concentration of PA was always higher than that of FL. No phase I or phase II metabolites were detected for either compound, even in the bile. Concentrations and total tissue burdens were higher in the internal organs than in the muscle for PA and FL. The highest levels of PA equivalent to 5 days' feeding were present in internal organs on week 10. Levels of PY were lower than levels of FL in internal organs and muscle. The amounts of PY-glucuronide in whole gall bladder bile were higher than amounts of PY in any whole compartment. PY-glucuronide was also detected in internal organs. Comparison will be made to a short-term exposure of winter flounder to 5 μg/g of the same three PAHs.     

One-step synthesis and solvent-induced exfoliation of hybrid organic-inorganic phyllosilicate-like materials

A room-temperature sol-gel-based process was used to produce by direct synthesis talc-like organosilicates having hexadecyl or aminopropyl groups pending in the interlayer space. Thermal analyses, Fourier transform infrared and 13C/29Si solid-state nuclear magnetic resonance spectroscopies confirmed the presence of organic moieties bonded to the inorganic network. Exfoliation of these organoclays in polar solvents such as water for the positively charged magnesium phyllo(aminopropyl)silicate, and in low polar solvents such as toluene and chloroform for hydrophobic magnesium phyllo(hexadecyl)silicate, was investigated by TEM. The ability of these layered magnesium organosilicates to exfoliate in appropriate solvents was exploited for the preparation of transparent self-supporting films and ordered macroporous networks using by latex colloidal crystal templates.     

Influence of chain flexibility and crosslink density on mechanical properties of epoxy/amine networks

Blends of a bisphenol A diglycidyl ether prepolymer and an aliphatic diepoxy diluent crosslinked with a cycloaliphatic diamine were studied. These model networks have the characteristic that the crosslink density and the chain flexibility increase with the amount of diluent. These combined effects were studied by observing their mechanical properties. The decreases in the Young's modulus and the ultrasonic modulus were associated with the secondary thermomechanical relaxations that have been recorded and identified. Pre-plastic and plastic behaviors were discussed in terms of flexibility and crosslink density. A linear relationship was established between pre-plastic activation volume and crosslink density at temperatures lower than the activation of molecular chain motions responsible for the sub-T_g relaxations. At 0°C, a temperature above these secondary transitions, the higher the flexibility, the more defect nucleation and propagation increased. The work hardening rate and the upper yield stress decreased as the amount of diluent was increased. Fracture toughness was improved as the amount of diluent was increased. Crack propagation was related to the ability of the networks to deform plastically.     

Long-term effects of neonatal damage to the hippocampal formation and amygdaloid complex on object discrimination and object recognition in rhesus monkeys (Macaca mulatta).

Rhesus monkeys with neonatal aspiration lesions of the hippocampal formation or the amygdaloid complex were tested on concurrent discrimination learning (24-hr intertrial interval [ITI]) at 3 months, on object recognition memory (delayed nonmatching-to-sample [DNMS]) at 10 months, and retested on both tasks at 6–7 years of age. Neonatal amygdaloid damage mildly impaired acquisition at the 24-hr ITI and the performance test of DNMS at both ages. In contrast, early hippocampal lesions impaired performance only on the longest lists of 10 items in DNMS in adult monkeys. Thus, early amygdala lesions appeared to have resulted in a greater object memory loss than early hippocampal lesions. However, in light of recent findings from lesion studies in adult monkeys, the object memory impairment after early amygdaloid lesions is better accounted for by damage to the entorhinal and perirhinal cortex than by damage to the amygdaloid nuclei. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Lipid Emulsions Differentially Affect LPS-Induced Acute Monocytes Inflammation: In Vitro Effects on Membrane Remodeling and Cell Viability

The aim of this study was to assess how lipid emulsions for parenteral nutrition affect lipopolysaccharide (LPS)‐induced acute monocyte inflammation in vitro. An 18 h long LPS induced human monocyte leukemia cell stimulation was performed and the cell‐growth medium was supplemented with three different industrial lipid emulsions: Intralipid^®, containing long‐chain triglycerides (LCT—soybean oil); Medialipid^®, containing LCT (soybean oil) and medium‐chain triglycerides (MCT—coconut oil); and SMOFlipid^®, containing LCT, MCT, omega‐9 and ‐3 (soybean, coconut, olive and fish oils). Cell viability and apoptosis were assessed by Trypan blue exclusion and flow cytometry respectively. Monocyte composition and membrane remodeling were studied using gas chromatography and NR12S staining. Microparticles released in supernatant were measured by prothrombinase assay. After LPS challenge, both cellular necrosis and apoptosis were increased (threefold and twofold respectively) and microparticle release was enhanced (sevenfold) after supplementation with Medialipid^® compared to Intralipid^®, SMOFlipid^® and monocytes in the standard medium. The monocytes differentially incorporated fatty acids after lipid emulsion challenge. Finally, lipid‐treated cells displayed microparticles characterized by disrupted membrane lipid order, reflecting lipid remodeling of the parental cell plasma membrane. Our data suggest that lipid emulsions differentially alter cell viability, monocyte composition and thereby microparticle release. While MCT have deleterious effects, we have shown that parenteral nutrition emulsion containing LCT or LCT and MCT associated to n‐3 and n‐9 fatty acids have no effect on endotoxin‐induced cell death and inflammation.     

Plasticizing and Reinforcing Features of Siloxane Domains in Amine‐Cured Epoxy/Silica Hybrids

Organic/inorganic hybrid materials comprising an amine‐epoxide network and siloxane domains are produced by the sol/gel method. The presence of both plasticizing flexible linear siloxane sequences and reinforcing nanosized silica particles and branched silsesquioxanes (SSQO) structures is confirmed by ²⁹Si NMR and SAXS analysis. The hybrids display simultaneously a monotonical reduction in T_g and an increase in rubbery plateau modulus with increasing siloxane content. At the same time, nanoindentation tests reveal an improved resistance to plastic deformation. The effect of siloxane content on the values of the rubbery plateau modulus is evaluated through the EBM model for blends and composites exhibiting the characteristic co‐continuity of the two constituent phases.